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Lanthanide complexes with a tripodal nitroxyl radical showing strong magnetic coupling.pdf (1.2 MB)

Lanthanide Complexes with a Tripodal Nitroxyl Radical Showing Strong Magnetic Coupling

preprint
revised on 15.08.2020, 11:43 and posted on 17.08.2020, 07:56 by Mauro Perfetti, Andrea Caneschi, Taisiya S. Sukhikh, Kira E. Vostrikova
A series of isomorphous mononuclear complexes of Ln(III) ions comprising one stable tripoidal oxazolidine nitroxyl radical were obtained in acetonitrile media starting from nitrates. The compounds, [LnRad(NO3)3] (Ln = Gd, Tb, Dy, Tm, Y; Rad = 4,4-dimethyl-2,2-bis(pyridin-2-yl)-1,3-oxazolidine-3-oxyl), have molecular structure. Their coordination polyhedron, LnO7N2, can be described as a tricapped trigonal prism with symmetry close to D3h. The value of 23 cm-1 for the antiferromagnetic coupling Gd-Rad established from the DC magnetic and EPR data is a record strength for the complexes of 4f-elements with nitroxyl radicals. The terbium derivative displays frequency-dependent out-of-phase signals in zero field indicating single-molecule magnetic behavior with an effective barrier of 57 cm-1.

Funding

RFBR, research project № 20-33-70172

History

Email Address of Submitting Author

vosk@niic.nsc.ru

Institution

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Country

Russia

ORCID For Submitting Author

0000-0003-0989-0524

Declaration of Conflict of Interest

no conflict interests

Version Notes

second version

Exports